Enhancing Ni oxidation reconstruction in Ni3Fe nanoalloy for efficient Electro-Oxidation of 5-Hydroxymethylfurfural

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2024-11, Vol.499, p.156320, Article 156320
• Main Authors: Xiong, Yongzhi, Hu, Shengchun, Jiang, Jianchun, Liu, Yajun, Zhao, Wei, Ji, Xialin, Chen, Changzhou, Fan, Mengmeng, Wang, Kui
• Format: Article
• Language: English
• Subjects: Ball-milling; Electro-oxidation; HMF; Ni3Fe nanoalloy catalyst
• ISSN: 1385-8947
• DOI: 10.1016/j.cej.2024.156320

•A novel ball-milling strategy is presented for macroscopic preparation of Ni3Fe nanoalloy catalyst (Ni3Fe@NC).•The non-electrochemical process of HMFOR on Ni3Fe@NC was demonstrated.•The reaction processes of HMFOR on Ni@NC, Ni3Fe@NC, and Fe@NC after reconstruction were analyzed using DFT.•The D-band-center of Ni@NC, Ni3Fe@NC, and Fe@NC was analyzed. Herein, a novel ball milling-pyrolysis strategy was proposed for preparing a highly dispersed Ni3Fe nanoalloy catalyst (Ni3Fe@NC) used for 5-hydroxymethylfurfural (HMF) electro-oxidation reaction. The Ni3Fe@NC delivered a high current density of 100 mA cm−2 at a low potential of 1.467 V vs RHE, with a HMF conversion rate of over 99.6 %, 2,5-furan dicarboxylic acid (FDCA) selectivity of 97.1 % and a Faraday efficiency of 96.7 %. Theoretical calculations, in-situ EIS, quasi-in-situ XRD and XPS demonstrated that Fe-doping optimizes the electronic structure of Ni3Fe@NC and regulates its d-band center, which not only promoted the reconstruction of Ni3Fe@NC to form high-oxidation-activity Ni2+δ and Ni3+δ species but also reduced the reaction barrier of the key rate-determining step (*5-Hydroxymethyl-2-furancarboxylic acid (HMFCA)→*5-formyl-2-furancarboxylic acid (FFCA)) during HMFOR. Based on this interesting work, we provided a facile macroscopic preparation strategy on highly dispersed nanoalloy catalyst for efficient electro-oxidation of HMF.